Antimicrobial compositions

ABSTRACT

A surface treatment composition includes a surface treatment agent and an antimicrobial mixture comprising oxidizable antimicrobial particles distributed throughout a film-forming agent.

FIELD OF THE INVENTION

The present invention relates generally to antimicrobial compositionsand more particularly to a surface treatment composition comprisingoxidizable antimicrobial particles.

BACKGROUND OF THE INVENTION

Application of cleaning agents to surfaces to clean soil and stains iswell known. Research dealing with exploring how antimicrobial andantifungal agents may be incorporated into cleaning agents for improvingtheir ability to control disease-causing bacteria has also beenconducted.

A number of inorganic materials have been shown to exhibit antimicrobialand/or antifungal properties. For example, metals such as silver,copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium andthallium, have been shown to exhibit such properties. While the reasonsfor this are not yet fully understood, it is thought that ionized formsof these metals interact with thiol containing proteins and DNA therebypreventing the normal biological functions of bacterial or fungal cells.

United States Patent Application Publication No. 20130234263 to Wasan etal. discloses nano-fluids as cleaning compositions for cleaning soiledsurfaces, and a method and formulation for their use. The disclosuredescribes nano-fluids comprising aqueous suspensions of hydrophilicnanoparticles or polymers, useful in soil removal from hard, semi-hardor soft surfaces, and particularly for improved removal of grass andgrease stains.

U.S. Pat. No. 7,081,441 to McDonald et al. discloses a composition forcleaning and/or treating surfaces. The composition comprises ananoparticles component selected from the group consisting of metaloxyhydroxides, modified metal oxyhydroxides and mixtures thereof; abuffer/modifier component; optionally an adjunct ingredient, and thebalance of the composition being a polar solvent. According to thedisclosure, the metal oxyhydrides in aqueous solution are converted intoand maintained as nanoparticulate sized modified metal oxyhydroxides. Inone aspect, a dry film results from contacting a surface with thecomposition that comprises greater than or equal to about 0.05 μg ofnanoparticles per cm² of treated surface.

In the publication entitled “Facile In-Situ Preparation of Poly(AcrylicAcid)-Silver Nanocomposite Thin Films with Highly Dispersed SilverNanoparticles” (Kim et al.) Mol. Cryst. Liq. Cryst. Vol 568: pp 170-178,2012, there is disclosed a method of preparing of PAA-Ag nanocompositethin films with highly dispersed Ag nanoparticles. During the method,silver salts are chemically reacted with acrylic acid, and as a resultsilver nanoparticles are produced in situ within an acrylic film.

In the publication entitled “In-situ Synthesis of Nano Silver ParticlesUsed in Obtaining of Antimicrobial Film-Forming Materials” (Pica et al.)REV. CHEM. (Bucharest) 63, No. 5, 2012, there is disclosed processes bywhich silver nanoparticles that are stable in time are obtained for usein formulating antimicrobial coating materials. Chemical synthesis ofthe silver nanoparticles comprises dissolving and reducing metals saltsin a polymer matrix.

U.S. Pat. No. 7,357,949 to Trogolo et al. discloses an encapsulatedinorganic antimicrobial additive for controlled release. Microcapsulescomprising an antimicrobial agent are encapsulated within a hydrophilicpolymer, which is capable of absorbing sufficient water as to enable theaction of the encapsulated antimicrobial agent. In this patent, theantimicrobial agent is a zeolite that retains metal ions until they areable to be released via ion exchange.

While it is known to provide surface cleaning compositions thatincorporate antimicrobial agents, improvements for prolongedantimicrobial efficacy with cleaning compositions and other surfacetreatment compositions are desired.

SUMMARY OF THE INVENTION

According to an aspect, there is provided a surface treatmentcomposition comprising a surface treatment agent; and an antimicrobialmixture comprising oxidizable antimicrobial particles distributedthroughout a film-forming agent.

In one embodiment, the oxidizable antimicrobial particles arenanoparticles selected from the group consisting of silver, copper,zinc, gold, and combinations thereof.

In one embodiment, the film-forming agent forms a substantiallytransparent film on the surface to be treated.

According to another aspect, there is provided a surface treatmentcomposition comprising a transient component comprising a surfacetreatment agent; and a residual component carried by the transientcomponent for forming a film on a surface that comprises oxidizableantimicrobial particles distributed throughout.

According to another aspect, there is provided a surface treatmentcomposition comprising a residual component for forming, on a treatedsurface, a film that comprises oxidizable antimicrobial particlesdistributed throughout; and a transient component carrying the residualcomponent, wherein the film remains on the treated surface in the eventthat the transient component is removed.

According to another aspect, there is provided a method of use of anantimicrobial mixture in a surface cleaning composition, theantimicrobial mixture comprising oxidizable antimicrobial particlesdistributed throughout a film-forming agent, the method comprisingcombining the antimicrobial mixture with a surface cleaning agent andapplying the resultant composition to a surface.

According to another aspect, there is provided a surface cleaningcomposition incorporating oxidizable antimicrobial particles distributedthroughout a film-forming agent.

According to another aspect, there is provided a liquid-based cleaningcomposition incorporating oxidizable antimicrobial particles distributedthroughout a film-forming agent.

According to another aspect, there is provided a liquid-based cleaningcomposition for both cleaning and leaving a residual film on a surface,the residual film incorporating oxidizable antimicrobial particlesdistributed throughout.

According to another aspect, there is provided a liquid-based surfacetreatment composition for both cleaning and leaving a residual film on asurface, the residual film incorporating oxidizable antimicrobialparticles distributed throughout.

According to another aspect, there is provided a film-forming agenthaving copper and silver nanoparticles distributed throughout.

According to another aspect, there is provided a textile to which isbonded a film incorporating oxidizable antimicrobial particlesdistributed throughout.

According to another aspect, there is provided a printable compositioncomprising a film-forming agent incorporating oxidizable antimicrobialparticles distributed throughout.

According to another aspect, there is provided a surface treatmentcomposition comprising a film-forming agent comprising an acrylicpolymer emulsion; copper and silver nanoparticles distributed throughoutthe film-forming agent; and a surface treatment agent comprising water,surfactant, citrus terpenes and isopropyl alcohol.

According to another aspect, there is provided a surface treatmentcomposition comprising: a film-forming agent comprising a siliconeemulsion; copper and silver nanoparticles distributed throughout thefilm-forming agent; and a surface treatment agent comprising paraffinwax, polyethylene wax, citrus terpenes, dimethyl ethanol amine, and ade-foaming agent.

According to another aspect, there is provided a surface treatmentcomposition comprising a film-forming agent comprising a polyurethaneemulsion; copper and silver nanoparticles distributed throughout thefilm-forming agent; and a surface treatment agent comprising silicone,polyethylene wax, paraffin wax, and a de-foaming agent.

The compositions provided herein form a thin solid film that binds to atarget surface. Oxidizable antimicrobial particles are distributedthroughout the film. The oxidizable antimicrobial particles continue toproduce new ions for interfering with biological processes of proximatebacteria and fungi. Furthermore, the oxidizable antimicrobial particlesdo not require ion exchange conditions in order to produce ions that areharmful to disease-causing bacteria and the like. Furthermore, becausethe oxidizable antimicrobial particles are distributed throughout thefilm, antimicrobial activity at the surface continues for as long assome of the film remains on the surface. Thus, even if some oxidizableantimicrobial particles are carried away from the surface along withparts of the film that are gradually worn away over time due to abrasionor the like, other oxidizable antimicrobial particles will remain alongwith remainder of the film.

BRIEF DESCRIPTION OF THE DRAWING

Embodiments of the invention will now be described with reference to theappended drawings in which:

FIG. 1 depicts a surface upon which a film having oxidizableantimicrobial particles distributed throughout has been formed; and

FIG. 2 depicts the film having been partially worn away due to abrasion.

DETAILED DESCRIPTION

Turning now to FIG. 1, there is shown a surface 10 upon which a thinsolid film 12 containing oxidizable antimicrobial particles 14distributed throughout has been formed. The film 12 binds to surface 10and the oxidizable antimicrobial particles 14 thereby remain associatedwith surface 10 available as an antimicrobial as long as there remainson the surface some film 12. Surface 10 may be a floor, a table, adoorknob, a sink, a faucet handle, a container, a textile, a fabric orsome other surface that is desired to be treated.

FIG. 2 depicts the film 12, at some time after treatment, having beenpartially worn away due to abrasion occurring during normal use ofsurface 10. It can be seen that, despite the abrasion having caused theremoval from the surface of several oxidizable antimicrobial particlesalong with portions of the film 12, the same abrasion has also resultedin exposure of other oxidizable antimicrobial particles that can providecontinue to provide antimicrobial function. The amount of time that theoxidizable antimicrobial particles 14 can be effective at the surface 10corresponds to the amount of time that the film 12 containing theparticles can remain bonded to the surface 10. Thus, the greater theextent of the abrasion, the faster the film 12 will deplete, accordinglydepleting the numbers of oxidizable antimicrobial particles 14.Similarly, if there is no or very little abrasion, the slower the film12 will deplete, and the numbers of oxidizable antimicrobial particles14 will accordingly remain higher for a longer period of time. Becausethe oxidizable antimicrobial particles 14 themselves continuouslyproduce antimicrobial ions, antimicrobial interference persists as longas the oxidizable antimicrobial particles 14 remain bonded by the film12 to the surface 10.

It will be understood that FIGS. 1 and 2 are cross-sectional drawingsdepicting a thin slice of the surface 10, the film 12 and the oxidizableantimicrobial particles 14 distributed uniformly throughout as ispreferred. It will be understood that oxidizable antimicrobial particles14 may be non-uniformly distributed throughout, while still providingprolonged antimicrobial benefits. It will also be understood that theabrasions and pits created in the film 12 over time may have manydifferent shapes and sizes. It is even possible that such abrasions/pitsmay be made deeply, such that they extend into surface 10 fully removinga section of film 12 and the oxidizable antimicrobial particles 14distributed in the section. It will be understood that subsequentapplication of a film-forming material for producing a film 12 willcause the film to form along the surfaces of the abrasions/pits in thesurface 10 to provide antimicrobial action therein.

According to the invention the film 12, along with the oxidizableantimicrobial particles 14 distributed throughout, is formed on surface10 by application to surface 10 of a surface treatment composition. Thesurface treatment composition includes a surface treatment agent and anantimicrobial mixture comprising oxidizable antimicrobial particlesdistributed throughout a film-forming agent.

Cleaner

In an embodiment, the oxidizable antimicrobial particles 14 compriseboth silver and copper nanoparticles in ratio of 1:30 by weight.Variations are possible. The copper and silver nanoparticles have anaverage diameter of about 100 nanometres, though variations arepossible. It is preferred that the nanoparticles have a weight andsurface area that enables the nanoparticles to remain substantiallysuspended within the surface treatment composition after preparation soas to remain distributed throughout.

In this embodiment, the film-forming agent is an acrylic polymeremulsion that, when applied to a hard, smooth surface such as a metaltable, ceramic sink or metal faucet forms a thin, hard, durable acrylicfilm. During preparation of the antimicrobial mixture a pre-mixturehaving 0.2% by weight copper nanoparticles, 6% by weight silvernanoparticles and 93.8% by weight water is prepared. The pre-mixture isagitated to distribute the nanoparticles throughout the water, and isthen combined with the acrylic polymer emulsion. This combination isagitated thereby to result in the film-forming agent with the oxidizableantimicrobial particles distributed throughout.

In this embodiment, the surface treatment agent is a cleaner that servesalso as a transient component of the surface treatment composition thatcarries the film-forming agent. The surface treatment agent compriseswater, surfactant, citrus terpenes, and isopropyl alcohol. The surfacetreatment agent and the film-forming agent with oxidizable antimicrobialparticles distributed throughout are then combined to provide an amountof antimicrobial particles in the composition to produce anantimicrobially-effective amount of oxidizable antimicrobial particlesdistributed throughout a resultant film.

The cleaner in this embodiment is referred to as a transient componentof the surface treatment composition because, after the cleaner hasdealt with stains and soiling and disinfection at the surface, it can beremoved entirely for example by wiping away. The film-forming agent bycomparison is the residual component of the surface treatmentcomposition because it forms a film that remains bonded to a surfaceeven after the cleaner is entirely removed. In this embodiment, thefilm-forming agent leaves a thin, solid, substantially transparent hardfilm on the surface.

It is preferred that there be a nanoparticle concentration in thesurface treatment composition of about 150 ppm silver nanoparticles(0.0150%) and 75 ppm copper nanoparticles (0.0075%). Thus, for example,for silver nanoparticles, one could employ a 55 gallon drum, which holds210 kilograms (kg) of water. If solids are at 3% then this correspondsto 6.3 kg (6300 grams) of solids in the drum. To calculate the silvermass, the product of: 6300 grams×0.0150% equals about 1 grams of silverper drum. At about 30% silver by weight, one adds about 3.3 grams ofpre-mixture to get 1 gram of silver in the drum.

Higher solids percentage could be calculated proportionally, forexample, 30% solids would require 33 grams of pre-mixture per 55 gallondrum.

It will be understood that the oxidizable antimicrobial particles 14 maybe of different types, having different sizes and various relativeconcentrations. The oxidizable antimicrobial particles 14 are referredto as such because these particles, in ionized form, interact with thiolcontaining proteins and DNA thereby preventing the normal biologicalfunctions of bacterial or fungal cells.

While, in this embodiment, the oxidizable antimicrobial particles aresilver and copper nanoparticles, it will be appreciated that other metalnanoparticles, such as zinc, titanium, gold and combinations of zinc,titanium, gold, copper and silver or other materials may be employed asalternatives or in some combination.

Hard Surface Protectant

In an alternative embodiment, the antimicrobial pre-mixture has the samenanoparticle composition as that described above, and the film-formingagent is an acrylic polymer emulsion that, when applied to a hard,smooth surface such as glass, ceramic or the like forms a thin, hard,durable and substantially transparent acrylic film. The pre-mixture isagitated to distribute the nanoparticles throughout the water, and isthen combined with the acrylic polymer emulsion. This combination isagitated thereby to result in the film-forming agent with the oxidizableantimicrobial particles distributed throughout.

In this embodiment, the surface treatment agent is as described above,and additionally includes ammonia.

It will be understood that in this embodiment also, the oxidizableantimicrobial particles 14 may be of different types, having differentsizes and various relative concentrations. While, in this embodiment,the oxidizable antimicrobial particles are silver and coppernanoparticles, it will be appreciated that other metal nanoparticles,such as zinc, titanium, gold and combinations of zinc, titanium, gold,copper and silver or other materials may be employed as alternatives orin some combination.

Polish and Protectant

In an alternative embodiment, the antimicrobial pre-mixture has the samenanoparticle composition as that described above, and the film-formingagent is a silicone emulsion that, when applied to various surfaces suchas wood, vinyl and leather forms a thin, durable and substantiallytransparent silicone film. The pre-mixture is agitated to distribute thenanoparticles throughout the water, and is then combined with thesilicone emulsion. This combination is agitated thereby to result in thefilm-forming agent with the oxidizable antimicrobial particlesdistributed throughout.

In this embodiment, the surface treatment agent is both a polishingagent and a protectant. The surface treatment agent comprises paraffinand polyethylene waxes, citrus terpenes, dimethyl ethanol amine (DMEA)as a rewetting agent, and a de-foaming agent. The surface treatmentagent and the film-forming agent with oxidizable antimicrobial particlesdistributed throughout are then combined to provide an amount ofantimicrobial particles in the composition to produce anantimicrobially-effective amount of oxidizable antimicrobial particlesdistributed throughout a resultant film.

It will be understood that in this embodiment also, the oxidizableantimicrobial particles 14 may be of different types, having differentsizes and various relative concentrations. While, in this embodiment,the oxidizable antimicrobial particles are silver and coppernanoparticles, it will be appreciated that other metal nanoparticles,such as zinc, titanium, gold and combinations of zinc, titanium, gold,copper and silver or other materials may be employed as alternatives orin some combination.

One or both of the waxes may be present.

Sealant

In an alternative embodiment, the antimicrobial pre-mixture has the samenanoparticle composition as that described above, and the film-formingagent is a polyurethane emulsion that, when applied to uneven or poroussurfaces such as wood or concrete produces a durable and substantiallytransparent film over the surface. The pre-mixture is agitated todistribute the nanoparticles throughout the water, and is then combinedwith the polyurethane emulsion. This combination is agitated thereby toresult in the film-forming agent with the oxidizable antimicrobialparticles distributed throughout.

In this embodiment, the surface treatment agent is a sealant. Thesurface treatment agent comprises silicone, polyethylene wax, paraffinwax, and a de-foaming agent. The surface treatment agent and thefilm-forming agent with oxidizable antimicrobial particles distributedthroughout are then combined to provide an amount of antimicrobialparticles in the composition to produce an antimicrobially-effectiveamount of oxidizable antimicrobial particles distributed throughout aresultant film.

It will be understood that in this embodiment also, the oxidizableantimicrobial particles 14 may be of different types, having differentsizes and various relative concentrations. While, in this embodiment,the oxidizable antimicrobial particles are silver and coppernanoparticles, it will be appreciated that other metal nanoparticles,such as zinc, titanium, gold and combinations of zinc, titanium, gold,copper and silver or other materials may be employed as alternatives orin some combination.

One or both of the waxes may be present.

Printed Coatings

It has been found that a composition made by combining a film-formingagent such as acrylic polymer, a urethane emulsion or a colloidal-basedcoating with oxidizable antimicrobial particles such as described abovecan produces substantial benefits in providing antimicrobial andantifungal protection for packages. Advantageously, coatings forpackaging including these film-forming agents with oxidizableantimicrobial nanoparticles distributed throughout along with waxes,de-foaming agents and amines, can be easily integrated into the printingprocess for product packaging, such that costs of integration ofantimicrobial protection can thereby be kept low. Substantialantimicrobial and antifungal benefits would be realized in a retailenvironment. For example, the antimicrobial benefits of the compositionsdescribed above are advantageous when used with packaging containing acough medicine were coated as described above, as consumers handlingsuch packaging when considering it for purchase may leave behinddisease-causing microbes.

Textiles

The dyeing of yarn and textiles is done with a solution containingpigments and particular chemical materials depending on the type offibers being dyed. For example, acrylic fibers are dyed with basic dyes.Nylon, wool and silk are dyed with acid dyes. Polyester is dyed withdisperse dyes. Cotton is dyed with a range of dye types, including vatdyes, and modern synthetic dyes). During the dye process thenanoparticles form a chemical bond with fiber molecules.

Tests Conducted

Cleaner:

A pre-saturated or impregnated towelette was used to wipe hard surfacescontaminated with Staphylococcus epidermidis (ATCC #12228) andEscherichia coli (ATCC# 8739) respectively. Wiped surfaces showed areduction of 99.85% against S. epidermidis and a reduction of 99.72%against E. coli after twenty-four (24) hours relative to unwipedsurfaces (control).

Hard Surface Protectant:

Testing was conducted on laminated writing shelves contaminated withStaphylococcus epidermidis (ATCC #12228). Treated surfaces showedreductions of 94.4% and 80.4% against S. epidermidis after twenty-four(24) hours, while untreated surfaces (control) showed no reduction.

Printed coatings (Papers):

Medical papers treated with the surface treatment agent were testedagainst Escherichia coli (ATCC25922) and Pseudomonas aeruginosa(ATCC27853) respectively. Treated medical papers showed a reduction of99.99% after twenty-four (24) hours, while non treated medical papers(control) showed no reduction.

Printed coatings (Cartons):

Cartons of 2.5 cm×2.5 cm area were treated with one layer of thefilm-forming agent and tested against Escherichia coli (ATCC25922) andPseudomonas aeruginosa (ATCC27853) respectively. Treated cartons showedreductions of 99.99% against E. coli and P. aeruginosa after twenty-four(24) hours, while non-treated cartons (control) showed no reduction.

Textiles:

Textiles in a variety of products were tested: Military cotton socks,Black Acrylic Socks, White Cotton Socks, Tan Cotton Socks, BlackAcrylic/Polyester Socks, Green Cotton Socks, Wool Socks, Black CottonSocks, Yellow Spun Polyester Socks, White Cotton Pillowcase, GreenPolyester Knit, Cotton Nylon Headwear, Black Polyester Socks, BlackPolyester Fabric, and Military Blue Polyester Shirts. These textileswere tested against Staphylococcus aureus (ATCC6538), KlebsiellaPneumoniae (ATCC4352), and C. albicans (ATCC10231) using a sample sizeof 48±1 mm diameter containing one layer of the film-forming agent. Areduction of 99.99% was observed all after 0, 15, 30 and 50 washesrelative to untreated material.

Textiles such as Blue Mattress Ticking Fabric, Polyester Seat Cover,Shoes Liner and Polyester Yarn showed 99.99% reduction of microbes aftertwenty-four (24) hours treatment (zero (0) washes) relative to untreatedmaterial.

It is to be noted that the textile tests were performed using LetheenBroth developed as a subculture medium for the neutralization ofquaternary ammonium compounds and other preservatives in disinfectanttesting.

While embodiments described above include copper and silvernanoparticles in combination and a particular ratio, variations arepossible. For example, the copper and silver particles may be providedin different ratios, or copper may be provided alone or in combinationwith other suitable oxidizable antimicrobial particles. Similarly,silver may be provided along or in combination with other suitableoxidizable antimicrobial particles. Other suitable oxidizableantimicrobial particles include particles of metals such as zinc,titanium and gold. Furthermore, while metals of the sort described abovetend to readily create antimicrobial ions due to ready loss ofelectrons, other inorganic materials that work substantially the sameway to produce substantially the same result, perhaps with faster orslightly slower emission of such antimicrobial ions, may be employed.

It will also be understood that while circles in the figures depictspherical nanoparticles, nanoparticles of different shapes, such asrods, triangles, spheres, and so forth, may be used.

Although embodiments have been described with reference to the drawings,those of skill in the art will appreciate that variations andmodifications may be made without departing from the spirit and scopethereof as defined by the appended claims.

1. A surface treatment composition comprising: a surface treatmentagent; and an antimicrobial mixture comprising oxidizable antimicrobialparticles distributed throughout a film-forming agent.
 2. The surfacetreatment composition of claim 1, wherein the oxidizable antimicrobialparticles are uniformly distributed throughout the film-forming agent.3. The surface treatment composition of claim 1, wherein the oxidizableantimicrobial particles are nanoparticles.
 4. The surface treatmentcomposition of claim 3, wherein the nanoparticles are metalnanoparticles.
 5. The surface treatment composition of claim 4, whereinthe nanoparticles are selected from the group consisting of: silvernanoparticles, copper nanoparticles, zinc nanoparticles, titaniumnanoparticles, gold nanoparticles, and combinations thereof.
 6. Thesurface treatment composition of claim 4, wherein the nanoparticlescomprise one or more of: silver nanoparticles, copper nanoparticles,zinc nanoparticles, gold nanoparticles, titanium nanoparticles.
 7. Thesurface treatment composition of claim 4, wherein the nanoparticlescomprise silver nanoparticles and copper nanoparticles.
 8. The surfacetreatment composition of claim 7, wherein the nanoparticles comprise a1:30 ratio by weight of copper nanoparticles to silver nanoparticles. 9.The surface treatment composition of claim 8, wherein the coppernanoparticles have a diameter of about 100 nanometres.
 10. The surfacetreatment composition of claim 8, wherein the silver nanoparticles havea diameter of about 100 nanometres.
 11. The surface treatmentcomposition of claim 1, wherein the film-forming agent forms a polymericfilm on the surface when the surface treatment composition is applied toa surface.
 12. The surface treatment composition of claim 11, whereinthe film-forming agent comprises acrylic acid.
 13. The surface treatmentcomposition of claim 1, wherein the film-forming agent comprisessilicone, wherein the silicone further functions as at least one of: asealant, a protectant.
 14. The surface treatment composition of claim13, wherein the film-forming agent further comprises a rewetting agent.15. The surface treatment composition of claim 14, wherein the rewettingagent is dimethyl ethanol amine (DMEA).
 16. The surface treatmentcomposition of claim 1, wherein the surface treatment agent comprises asurface cleaning agent.
 17. The surface treatment composition of claim16, wherein the surface cleaning agent comprises isopropyl alcohol. 18.The surface treatment composition of claim 16, wherein the surfacecleaning agent comprises water, isopropyl alcohol, surfactant and citrusterpenes.
 19. The surface treatment composition of claim 1, wherein thesurface treatment agent comprises at least one of: a surface polishingagent, a surface protectant.
 20. The surface treatment composition ofclaim 1, wherein the surface treatment agent comprises at least one of:paraffin wax, polyethylene wax.
 21. The surface treatment composition ofclaim 1, wherein the surface treatment agent comprises a surfacesealant.
 22. The surface treatment composition of claim 1, wherein thefilm-forming agent forms a substantially transparent film.
 23. Thesurface treatment composition of claim 1, further comprising: atransient component comprising the surface treatment agent; and aresidual component comprising the antimicrobial mixture. 24-38.(canceled)